EP0076493A2 - Use of 1,1-di(C1-C6-alkyl)-2-phenyl-ethane derivatives as aroma chemicals - Google Patents

Use of 1,1-di(C1-C6-alkyl)-2-phenyl-ethane derivatives as aroma chemicals Download PDF

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EP0076493A2
EP0076493A2 EP82109101A EP82109101A EP0076493A2 EP 0076493 A2 EP0076493 A2 EP 0076493A2 EP 82109101 A EP82109101 A EP 82109101A EP 82109101 A EP82109101 A EP 82109101A EP 0076493 A2 EP0076493 A2 EP 0076493A2
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Prior art keywords
phenyl
alkyl
fragrance
aldehyde
dimethyl
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German (de)
French (fr)
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EP0076493A3 (en
EP0076493B1 (en
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Ernst-Joachim Dr. Brunke
Erich Dr. Klein
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Dragoco Gerberding and Co GmbH
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Dragoco Gerberding and Co GmbH
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
    • C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C33/00—Unsaturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C33/18—Monohydroxylic alcohols containing only six-membered aromatic rings as cyclic part
    • C07C33/20—Monohydroxylic alcohols containing only six-membered aromatic rings as cyclic part monocyclic
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B9/00—Essential oils; Perfumes
    • C11B9/0061—Essential oils; Perfumes compounds containing a six-membered aromatic ring not condensed with another ring

Definitions

  • the invention relates to the use of the 1,1-dialkyl-2-phenyl-ethane derivatives Aa-e, in which R is a formyl, hydroxymethyl, acetoxymethyl, nitrile or formoxymethyl group, as a fragrance or constituent of a fragrance mixture - Gen for cosmetic and technical perfumes in particular.
  • Fragrances with a floral odor characteristic are of great interest to perfumery. Since the distillates or extracts from parts of plants with the respective characteristic scent are either very expensive - such as, for example, with rose oil or ' jasmine absolute', or cannot be obtained due to their instability - as is the case with lilac or lily-of-the-valley The existence of the fragrance industry strives to represent synthetic substitute products.
  • the secondary alcohols analogous to the tertiary alcohols 2 and 3 are not used in perfumery, but the corresponding primary alcohols 4 and 5 are, however, used. However, these compounds have significantly different odor notes from 2, 3.
  • the fragrance of phenylethyl alcohol (4) used in large quantities is described as "mild and warm, rose and honey-like" (Arctander, No. 2513).
  • the dihydrocinnamic alcohol (5) smells a little cinnamon-like, or "warm and mild, balsamic-flowery, sweet" (Arctander, No. 2589).
  • the ⁇ -methyl-dihydro-cinnamon alcohol (6) which is represented by aldol condensation of benzaldehyde and propionaldehyde and subsequent hydrogenation, has a very weak, cinnamon-sweet, slightly woody smell and is not used as a fragrance.
  • the ⁇ , ⁇ -dimethyl-substituted primary alcohol Ib has a strongly radiating and pleasantly floral fragrance in the direction of lily of the valley and hyacinth, which is pronounced of certain odor aspects of the tertiary carbinols, but surpasses them in natural perfume compositions .
  • the ⁇ , ⁇ -dimethyl compound Ib has been described in the chemical literature without its particular olfactory properties having been recognized or mentioned - [V. G. Purohit and R. Subramanian, Chem. And Ind. 1978, 731. P. Warrick and W. H. Saunders, J. Am. Chem. Soc., 84, 4095 (1962). A. Haller and E. Bauer, Ann. Chim., 9, 15 (1918)]. It has been found that compound 1b can be incorporated very well into perfume oils of a floral type due to their olfactory properties and gives them more natural charisma.
  • the aldehyde la has a strong aldehydic-green smell, which can be advantageously incorporated into perfume oils, especially in small doses.
  • the presentation of the ⁇ , ⁇ -dimethyl-substituted aldehyde la was described by H.K. Dietl and K.C. Brannock (Tetrahedron Letters 1973, 1273), without the odor properties of the compound having been discussed.
  • esters were prepared from the primary alcohol 1b by conventional esterification, of which the acetate 1e and the Formate le have special olfactory effects.
  • the scents of 1c can be described as "woody, sweet-herbaceous, flowery” and those of le as “woody, herbaceous, green”.
  • the Nitrile Id has a herb-balsamic fragrance with floral and fruity side notes.
  • the compounds la-ld are accessible from basic chemicals in a relatively simple way and can therefore be produced in any quantity.
  • the substances la-d were prepared starting from benzylcioloride (7), which was converted in a "phase transfer" reaction with isobutyraldehyde (8) to the aldehyde 1a in a manner known per se. This reaction is using 50%.
  • aqueous sodium hydroxide solution and catalytic amounts of tetrabutylammonium iodide have been described (HK Dietl and KC Brannock, Tetrahedron Letters 1973, 1273). It has been found that, instead of the expensive tetrabutylammonium iodide used by Dietl and Brannock, the inexpensive tricapryl-methyl-ammonium chloride (Aliquat 336) can also be used.
  • the reaction is carried out at elevated temperature, preferably at boiling temperature, in a two-phase system consisting of toluene and 50% NaOH.
  • the aldehyde Ia was obtained in about 60% yield by customary working up and distillation.
  • the reduction of the aldehyde la to the primary alcohol 1b was carried out preferably by catalytic hydrogenation using Raney-nickel or copper-chromite in undiluted state or by using polar aprotic L ö - sungsstoffn such as methanol. Furthermore, the reduction was carried out using hydrides such as sodium borohydride or lithium aluminum hydride in compliance with customary reaction conditions.
  • esterification was carried out in a manner known per se by reacting the alcohol Ib with acid anhydrides in the presence of acid-binding substances such as sodium carbonate or potassium carbonate.
  • Acetate 1c was prepared by reacting Ib with acetic anhydride / sodium carbonate.
  • the nitrile ld was prepared in a manner known per se by the action of hydroxylamine on la in a basic medium to form the oxime 9 and its subsequent dehydration by the action of acetic anhydride at the boiling point.
  • a-alkyl-substituted aldehydes with a maximum of 10 carbon atoms such as 2-methyl-butanal, 2-methylpentanal, 2-ethyl-butanal, 2-ethyl-pentanal, .2-ethyl-hexanal, 2-propylpentanal
  • phase transfer catalysts preferably tricaprylammonium chloride and alkali hydroxides.
  • the resulting aldehydes of the general formula Aa have fresh and partly woody-herbaceous notes.
  • the acetates of the general Formal A C illustrated in analogy to 1 C have woody and sweet and herbaceous odor notes, while in analogy to ib resulting primary alcohols of the general formula Ab mild flowery, fresh smell have some aspects.
  • the nitriles of the general formula Ad obtained in analogy to ld have sweet-floral and herbaceous notes and the formate Ae fresh woody notes.
  • the olfactory aspects of the compounds Aa-d become heavier and less bright, sometimes also somewhat weaker in intensity than that of the dimethyl-substituted compounds la-d.
  • the fixing and rounding off odor effects are more pronounced in perfume compositions with a higher molecular weight.
  • the compounds of the general formulas Aa-Ae can be used advantageously for perfuming cosmetic and technical products.
  • the aldehyde IIIa with 15 carbon atoms corresponding to the general formula Aa was prepared from benzyl chloride (7) and ⁇ -ethylhexanal (12) according to the instructions given for Ia.
  • the smell notes can be described as light, herbaceous, fruity (agricultural aspects).
  • the alcohol IIb with a mild floral note was obtained by reduction analogously to lb.
  • the perfume oil of mixture a has a balanced lily of the valley fragrance.
  • the mixture b in which the alcohol 1b according to the invention was used instead of the carbinol 3, also has a harmonious lily of the valley fragrance complex, which, however, is distinguished from the mixture a by more body and natural charisma.
  • the perfume oil of mixture a has a fragrance complex of the fougere type with woody, bitter-sweet aspects.
  • the perfume oil b which also contains the new compound 1c, has a fragrance complex of a similar type, in which, however, a sweet-powdery note is emphasized and which at the same time has a clearly rounded and harmonious effect.
  • Perfume oil a has a balanced lilac scent.
  • the perfume oil obtained by replacing the odorless dipropylene glycol and using 15% of carbinol 1b has an even more intense and natural-looking lilac scent.
  • the incorporation of 5% of the nitrile ld leads to an original floral-fresh fragrance complex, emphasizing the herb-green aspects.
  • the perfume oil of composition a has a classic sweet-powdery note with woody and spicy aspects.
  • the mixture b obtained by adding the nitrile 1d according to the invention has a more harmonious and softer effect while emphasizing sweet-spicy side notes.
  • This perfume oil has a harmonious smell complex of the agrumen type with fresh green-herbaceous notes. After adding 100 parts of 2-benzyl-2-ethyl-hexanal (Ila), the perfume oil looks finer and more natural. at the same time, the fragrance complex is clearly fixed.
  • Ila 2-benzyl-2-ethyl-hexanal

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Fats And Perfumes (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Cosmetics (AREA)

Abstract

1. The use of 1,1-Di(C1 -C6 -alkyl)-2-phenyl-ethane derivatives of formula A see diagramm : EP0076493,P8,F3 a : R = CHO b : R = CH2 OH c : R = CH2 OAc d : R = CN e : R = CH2 OCHO wherein R is a formyl-, hydroxymethyl-, formoxymethyl-, acetoxymethyl- or nitrilo group and the total number of carbon atoms in both alkyl substituents together is 8 at most, as aroma chemicals or flavoring ingredient of perfume compositions for cosmetic or technical flavorings.

Description

Gegenstand der Erfindung ist die Verwendung der 1,1-Dialkyl-2-phenyl-ethan-Derivate Aa-e, worin R eine Formyl-, Hydroxymethyl-, Acetoxymethyl-,Nitril- oder Formoxymethylgruppe bedeutet, als Riechstoff oder Bestandteil von Riechstoff-Mischun- gen für insbesondere kosmetische und technische Parfümierungen.The invention relates to the use of the 1,1-dialkyl-2-phenyl-ethane derivatives Aa-e, in which R is a formyl, hydroxymethyl, acetoxymethyl, nitrile or formoxymethyl group, as a fragrance or constituent of a fragrance mixture - Gen for cosmetic and technical perfumes in particular.

Die Erfindung wird zunächst anhand der α,α-Dimethyl-Derivate la-ld erläutert.

Figure imgb0001
The invention is first explained with reference to the α, α-dimethyl derivatives la-Id.
Figure imgb0001

Für die Parfümerie sind Riechstoffe mit blumiger Geruchscharakteristik von großem Interesse. Da die Destillate oder Extrakte aus Pflanzenteilen mit dem jeweils charakteristischen Duft entweder sehr kostspielig sind - wie z.B, bei Rosen-Ö1 oder'Jasmin-Absolue- , oder aufgrund ihrer Instabilität nicht zu gewinnen sind - wie bei Flieder oder Maiglöckchen - , ist man seit Bestehen der Riechstoff-Industrie bestrebt, synthetische Ersatzprodukte darzustellen. Während es für die meisten der verschiedenen geruchsprägenden Substanzen aus den stabilen Pflanzen-Destillaten oder -Extrakten bereits chemische Partial- oder Totalsynthesen gibt, die auch oft tecgbusch realisierbar sind, kann bei den instabilen Naturdüften wie Maiglöckchen oder Flieder nur auf technisch stabile, synthetische Ersatzprodukte zurückgegriffen werden, die zwar eine vom Naturstoff abweichende Struktur, aber einen ähnlichen Duft aufweisen sollten. Derartige vielfach verwendete synthetische Riechstoffe mit blumigem Charakter sind z.B. Dimethylbenzyl-carbinol (2) oder Phenylethyl-dimethyl-carbinol (3). Der Duft der Verbzndung 2 wird beschrieben als krautig warm blumig, leicht animalisch mit einer Nebennote nach frisch geschnittenem Holz-und Anklängen von Lilien- und Holunderblütenduft (S. Arctander, Perfume and Flavor Chemicals, 1969, Nr. 989). Die Verbindung 3 (Arctander, Nr. 1043) besitzt einen blumig grünen, schwach krautigen und öligen Duft, der an Lilie und Hyazinthe erinnert. Beide Verbindungen 2, 3 sind nur durch Grignard-Reaktionen zugänglich, die einen relativ hohen technischen Aufwand erfordern.Fragrances with a floral odor characteristic are of great interest to perfumery. Since the distillates or extracts from parts of plants with the respective characteristic scent are either very expensive - such as, for example, with rose oil or ' jasmine absolute', or cannot be obtained due to their instability - as is the case with lilac or lily-of-the-valley The existence of the fragrance industry strives to represent synthetic substitute products. While it is already chemi for most of the different odorous substances from the stable plant distillates or extracts there are partial or total syntheses, which can often also be realized in a bush, can only be used with technically stable, synthetic substitute products for unstable natural fragrances such as lily of the valley or lilac, which should have a structure that differs from the natural product, but should have a similar fragrance. Such frequently used synthetic fragrances with a floral character are, for example, dimethylbenzylcarbinol (2) or phenylethyldimethylcarbinol (3). The scent of compound 2 is described as herbaceous, warm, floral, slightly animal with a side note of freshly cut wood and hints of lily and elderflower scent (S. Arctander, Perfume and Flavor Chemicals, 1969, No. 989). Compound 3 (Arctander, No. 1043) has a floral green, slightly herbaceous and oily fragrance that is reminiscent of lily and hyacinth. Both compounds 2, 3 are only accessible through Grignard reactions, which require a relatively high technical outlay.

Die zu den tertiären Alkoholen 2 und 3 analogen sekundären Alkohole werden in der Parfümerie nicht verwendet, wohl aber die entsprechenden primären AlKohole 4 und 5. Allerdings besitzen diese Verbindungen erheblich von 2, 3 abweichende Geruchsnoten.

Figure imgb0002
So wird der Duft des in großen Mengen verwendeten Phenylethylalkohols (4) als "mild und warm, Rosen- und Honig-artig" beschrieben (Arctander, Nr. 2513). Der Dihydrozimtalkohol (5) riecht etwas zimtartig, bzw. "warm und mild, balsamisch-blumig, süß" (Arctander, Nr. 2589). Der durch Aldolkondensation von Benzaldehyd und Propionaldehyd sowie anschließende Hydrierung dargestellte α-Methyl-dihydro-zimtalkohol (6) besitzt einen sehr schwachen, zimtartig-süßen, leicht holzigen Geruch und wird nicht als Riechstoff verwendet.The secondary alcohols analogous to the tertiary alcohols 2 and 3 are not used in perfumery, but the corresponding primary alcohols 4 and 5 are, however, used. However, these compounds have significantly different odor notes from 2, 3.
Figure imgb0002
 The fragrance of phenylethyl alcohol (4) used in large quantities is described as "mild and warm, rose and honey-like" (Arctander, No. 2513). The dihydrocinnamic alcohol (5) smells a little cinnamon-like, or "warm and mild, balsamic-flowery, sweet" (Arctander, No. 2589). The α-methyl-dihydro-cinnamon alcohol (6), which is represented by aldol condensation of benzaldehyde and propionaldehyde and subsequent hydrogenation, has a very weak, cinnamon-sweet, slightly woody smell and is not used as a fragrance.

Es ist daher überraschend, daß der α,α-dimethyl-substituierte primäre Alkohol lb einen stark ausstrahlenden und angenehm blu- migen Duft in Richtung Maiglöckchen und Hyazinthe aufweist, der an bestimmte Geruchsaspekte der tertiären Carbinole erinnert, diese jedoch in Parfümkompositionen an natürlicher Ausstrahlung übertrifft. Die α,α-Dimethyl-Verbindung lb ist in der chemischen Literatur beschrieben worden, ohne daß ihre besonderen olfaktorischen Eigenschaften erkannt oder erwähnt worden sind-[V. G. Purohit und R. Subramanian, Chem. and Ind. 1978, 731. P. Warrick und W. H. Saunders, J. Am. Chem. Soc., 84, 4095 (1962). A. Haller und E. Bauer, Ann. Chim., 9, 15 (1918)]. Es wurde gefunden, daß sich die Verbindung 1b aufgrund ihrer Geruchseigenschaften sehr gut in Parfümöle blumigen Typs einarbeiten läßt und diesen mehr natürliche Ausstrahlung verleiht.It is therefore surprising that the α, α-dimethyl-substituted primary alcohol Ib has a strongly radiating and pleasantly floral fragrance in the direction of lily of the valley and hyacinth, which is reminiscent of certain odor aspects of the tertiary carbinols, but surpasses them in natural perfume compositions . The α, α-dimethyl compound Ib has been described in the chemical literature without its particular olfactory properties having been recognized or mentioned - [V. G. Purohit and R. Subramanian, Chem. And Ind. 1978, 731. P. Warrick and W. H. Saunders, J. Am. Chem. Soc., 84, 4095 (1962). A. Haller and E. Bauer, Ann. Chim., 9, 15 (1918)]. It has been found that compound 1b can be incorporated very well into perfume oils of a floral type due to their olfactory properties and gives them more natural charisma.

Der Aldehyd la besitzt einen starken aldehydisch-grünen Geruch der vor allem in geringen Dosierungen vorteilhaft in Parfümöle eingearbeitet werden kann. Die Darstellung des α,α-dimethyl-substituierten Aldehyds la wurde von H. K. Dietl und K. C. Brannock (Tetrahedron Letters 1973, 1273) beschrieben, ohne daß auf die Geruchseigenschaften der Verbindung eingegangen worden ist.The aldehyde la has a strong aldehydic-green smell, which can be advantageously incorporated into perfume oils, especially in small doses. The presentation of the α, α-dimethyl-substituted aldehyde la was described by H.K. Dietl and K.C. Brannock (Tetrahedron Letters 1973, 1273), without the odor properties of the compound having been discussed.

Durch übliche Veresterung wurden aus dem primären Alkohol 1b verschiedene Ester dargestellt, von denen das Acetat 1e und das Formiat le besondere olfaktorische Effekte aufweisen. Die Geruchsnoten von 1c können als"holzig, süß-krautig, blumig" und die von le als "holzig, krautig, grün" beschrieben werden. Das Nitril Id besitzt einen krautig-balsamischen Duft mit blumigen und fruchtigen Nebennoten. Die Verbindungen la-ld sind aus Grundchemikalien auf relativ einfachem Weg zugänglich und können daher in beliebiger Menge produziert werden.

Figure imgb0003
Various esters were prepared from the primary alcohol 1b by conventional esterification, of which the acetate 1e and the Formate le have special olfactory effects. The scents of 1c can be described as "woody, sweet-herbaceous, flowery" and those of le as "woody, herbaceous, green". The Nitrile Id has a herb-balsamic fragrance with floral and fruity side notes. The compounds la-ld are accessible from basic chemicals in a relatively simple way and can therefore be produced in any quantity.
Figure imgb0003

Die Darstellung der Substanzen la-d erfolgte ausgehend von Benzylciolorid (7), das in einer "phase-transfer"-Reaktion mit Isobutyraldehyd (8) in an sich bekannter Weise zu dem Aldehyd 1a umgesetzt wurde. Diese Reaktion ist unter Verwendung von 50%ig. wässriger Natronlauge und katalytischen Mengen an Tetrabutylammonium-jodid beschrieben worden (H. K. Dietl und K. C. Brannock, Tetrahedron Letters 1973, 1273). Es wurde gefunden, daß anstelle des von Dietl und Brannock eingesetzten,kostspieligen Tetrabutylammonium-jodids auch das preiswerte Tricapryl-methyl-ammonium-chlorid (Aliquat 336) verwendet werden kann. Die Reaktion wird bei erhöhter Temperatur, vorzugsweise bei Siedetemperatur, in einem Zweiphasen-System, bestehend aus Toluol und 50%iger NaOH durchgeführt. Durch übliches Aufarbeiten und Destillation wurde der Aldehyd la in ca. 60% Ausbeute erhalten. Die Reduktion des Aldehyds la zu dem primären Alkohol 1b erfolgte vorzugsweise durch katalytische Hydrierung unter Verwendung von Raney-Nickel oder Kupfer-chromit in unverdünntem Zustand oder unter Verwendung von polaren aprotischen Lö- sungsmitteln wie Methanol. Weiterhin wurde die Reduktion unter Verwendung von Hydriden wie Natriumborhydrid oder Lithiumaluminiumhydrid unter Einhaltung üblicher Reaktionsbedingungen ausgeführt.The substances la-d were prepared starting from benzylcioloride (7), which was converted in a "phase transfer" reaction with isobutyraldehyde (8) to the aldehyde 1a in a manner known per se. This reaction is using 50%. aqueous sodium hydroxide solution and catalytic amounts of tetrabutylammonium iodide have been described (HK Dietl and KC Brannock, Tetrahedron Letters 1973, 1273). It has been found that, instead of the expensive tetrabutylammonium iodide used by Dietl and Brannock, the inexpensive tricapryl-methyl-ammonium chloride (Aliquat 336) can also be used. The reaction is carried out at elevated temperature, preferably at boiling temperature, in a two-phase system consisting of toluene and 50% NaOH. The aldehyde Ia was obtained in about 60% yield by customary working up and distillation. The reduction of the aldehyde la to the primary alcohol 1b was carried out preferably by catalytic hydrogenation using Raney-nickel or copper-chromite in undiluted state or by using polar aprotic L ö - sungsmitteln such as methanol. Furthermore, the reduction was carried out using hydrides such as sodium borohydride or lithium aluminum hydride in compliance with customary reaction conditions.

Die Veresterung erfolgte in an sich bekannter Weise durch Umsetzen des Alkohols lb mit Säureanhydriden in Gegenwart säurebindender Substanzen wie beispielsweise Natriumcarbonat oder Kaliumcarbonat. Durch Umsetzung von lb mit Acetanhydrid/ Natriumcarbonat wurde das Acetat 1c dargestellt.The esterification was carried out in a manner known per se by reacting the alcohol Ib with acid anhydrides in the presence of acid-binding substances such as sodium carbonate or potassium carbonate. Acetate 1c was prepared by reacting Ib with acetic anhydride / sodium carbonate.

Das Nitril ld wurde in an sich bekannter Weise durch Einwirkung von Hydroxylamin auf la in einem basischem Medium unter Bildung des Oxims 9 und dessen nachfolgende Dehydratisierung durch Einwirkung von Acetanhydrid in der Siedehitze dargestellt.The nitrile ld was prepared in a manner known per se by the action of hydroxylamine on la in a basic medium to form the oxime 9 and its subsequent dehydration by the action of acetic anhydride at the boiling point.

Die für die Darstellung der Verbindungen la-ld beschriebenen Reaktionsschritte lassen sich auf homologe Verbindungen übertragen. So lassen sich a-alkyl-substituierte Aldehyde mit maximal 10 Kohlenstoff-Atomen wie z.B. 2-Methyl-butanal, 2-Methylpentanal, 2-Ethyl-butanal, 2-Ethyl-pentanal,.2-Ethyl-hexanal, 2-Propylpentanal vorteilhaft unter Verwendung von "phase-transfer"-Katalysatoren, vorzugsweise Tricapryl-ammoniumchlorid und Alkalihydroxiden, mit Benzylchlorid alkylieren. Die hierbei erhaltenen Aldehyde der allgemeinen Formel Aa besitzen frische und z.T, holzig-krautige Noten. Die in Analogie zu 1C dargestellten Acetate der allgemeinen Formal AC besitzen holzige und süß-krautige Geruchsnoten, während die in Analogie zu ib erhaltenen primären Alkohole der allgemeinen Formel Ab mildblumige, z.T. frische Geruchsaspekte aufweisen. Die in Analogie zu ld erhaltenen Nitrile der allgemeinen Formel Ad besitzen süß-blumige t.nd krautige und die Formiate Ae frischholzige Noten.The reaction steps described for the preparation of the compounds la-ld can be transferred to homologous compounds. Thus, a-alkyl-substituted aldehydes with a maximum of 10 carbon atoms, such as 2-methyl-butanal, 2-methylpentanal, 2-ethyl-butanal, 2-ethyl-pentanal, .2-ethyl-hexanal, 2-propylpentanal, can be used advantageously alkylate with benzyl chloride using phase transfer catalysts, preferably tricaprylammonium chloride and alkali hydroxides. The resulting aldehydes of the general formula Aa have fresh and partly woody-herbaceous notes. The acetates of the general Formal A C illustrated in analogy to 1 C have woody and sweet and herbaceous odor notes, while in analogy to ib resulting primary alcohols of the general formula Ab mild flowery, fresh smell have some aspects. The nitriles of the general formula Ad obtained in analogy to ld have sweet-floral and herbaceous notes and the formate Ae fresh woody notes.

1 Das Verfahren zur Herstellung der erfindungsgemäss verwendeten Verbindungen kann ganz allgemein wie folgt zusammengefasst werden:

  • 5 Man setzt Benzylchlorid mit einem (X-verzweigten aliphatischen Aldehyd mit bis zu 10 Kohlenstoffatomen in einer an sich bekannten "phase-transfer"-Reaktion unter Verwendung von Alkalihydroxiden und quaternären Ammoniumsalzen, vorzugsweise Tricapryl-Ammoniumchlorid zum Aldehyd 10 Aa um;
  • Der hierbei erhaltene Aldehyd Aa wird gegebenenfalls in an sich bekannter Weise durch katalytische Reduktion unter Verwendung von Übergangsmetall-Katalysatoren, vorzugs-15 weise Raney-Nickel oder Kupferchromat zum Alkohol Ab reduziert;
  • Der hierbei erhaltene Alkohol Ab wird gegebenenfalls in an sich bekannter Weise zu Ac verestert, wobei man 20 Acetanhydrid in Gegenwart säurebindender Mittel wie Natrium- oder Kaliumcarbonat oder -acetat einwirken lässt, oder
  • Der in Stufe 1 erhaltene Aldehyd Aa wird gegebenenfalls 25 in an sich bekannter Weise mit Hydroxylamin zu dem entsprechenden Oxim umgesetzt und dieses vorzugsweise durch Einwirkung von Acetanhydrid in der Siedehitze zum Nitril Ad dehydratisiert;
  • 30 Der in Stufe 2 erhaltene Alkohol Ab wird gegebenenfalls in an sich bekannter Weise zu Ae umgesetzt.
1 The process for the preparation of the compounds used according to the invention can be summarized as follows:
  • 5 Benzyl chloride is reacted with an (X-branched aliphatic aldehyde having up to 10 carbon atoms in a known phase transfer reaction using alkali metal hydroxides and quaternary ammonium salts, preferably tricaprylammonium chloride to form the aldehyde 10 Aa;
  • The aldehyde Aa obtained is optionally reduced to the alcohol Ab in a manner known per se by catalytic reduction using transition metal catalysts, preferably Raney nickel or copper chromate;
  • The alcohol Ab obtained is optionally esterified to Ac in a manner known per se, 20 acetic anhydride being allowed to act in the presence of acid-binding agents such as sodium or potassium carbonate or acetate, or
  • The aldehyde Aa obtained in stage 1 is optionally reacted in a manner known per se with hydroxylamine to give the corresponding oxime and this is preferably dehydrated to the nitrile ad by the action of acetic anhydride at the boiling point;
  • 30 The alcohol Ab obtained in stage 2 is optionally converted to Ae in a manner known per se.

Mit zunehmendem Molekulargewicht werden die Geruchsaspekte der Verbindungen Aa-d schwerer und weniger hell, z.T. auch in der Intensität etwas schwächer als die der Dimethyl-substituierten Verbindungen la-d. Allerdings treten die fixierenden und abrundenden Geruchseffekte in Parfumkompositionen bei höherem Molekulargewicht stärker hervor. Aufgrund ihrer Geruchscharakteristiken, ihrer fixierenden Eigenschaften und ihrer Stabilität in kosmetischen und technischen Medien können die Verbindungen der allgemeinen Formeln Aa-Ae vorteilhaft zum Parfümieren kosmetischer und technischer Produkte verwendet werden.

Figure imgb0004
With increasing molecular weight, the olfactory aspects of the compounds Aa-d become heavier and less bright, sometimes also somewhat weaker in intensity than that of the dimethyl-substituted compounds la-d. However, the fixing and rounding off odor effects are more pronounced in perfume compositions with a higher molecular weight. On account of their olfactory characteristics, their fixing properties and their stability in cosmetic and technical media, the compounds of the general formulas Aa-Ae can be used advantageously for perfuming cosmetic and technical products.
Figure imgb0004

Der der allgemeinen Formel Aa entsprechende Aldehyd lla mit 15 Kohlenstoffatomen wurde aus Benzylchlorid (7) und a-Ethylhexanal (12) nach der für la gegebenen Vorschrift dargestellt. Die Geruchsnoten können mit hell, krautig, fruchtig (Agrumenaspekte) beschrieben werden. Durch Reduktion wurde analog zu lb der Alkohol llb mit mild-blumiger Note erhalten.The aldehyde IIIa with 15 carbon atoms corresponding to the general formula Aa was prepared from benzyl chloride (7) and α-ethylhexanal (12) according to the instructions given for Ia. The smell notes can be described as light, herbaceous, fruity (agricultural aspects). The alcohol IIb with a mild floral note was obtained by reduction analogously to lb.

Die anschließenden Beispiele erläutern die Darstellung der Verbindungen la-d und deren Anwendung in Parfümölen.The following examples explain the representation of the compounds la-d and their use in perfume oils.

Beispiel 1example 1 Darstellung von 2,2-Dimethyl-3-phenyl-propanal-1 (1a);Preparation of 2,2-dimethyl-3-phenyl-propanal-1 (1a);

Unter Rühren wurde eine Lösung von 224 g (4 mol) KOH und 10 g Tricapryl-methyl-ammonium-chlorid (Aliquat 336) in 125 g Wasser mit 200 mℓ Toluol versetzt und zum Sieden erhitzt. Bei fortwährendem Sieden wurde eine Lösung von 402 g (3.2 mol) Benzylchlorid (7) und 256 g (3.6 mol) Isobutyraldehyd innerhalb von 1 Stde. zugetropft. Nach 7 Stdn. Rühren bei Siedetemp. und Abkühlen auf Raumtemp. wurde mit 300 g Wasser ausgedünnt. Die wässrige Phase wurde mit Toluol extrahiert. Die vereinigten organischen Phasen wurden neutralgewaschen und eingeengt. Das Rohprodukt (510 g gelbes Öl) ergab bei Destillation über eine 60 cm Glasfüllkörperkolonne 354 g (69 %) laals farbloses Öl. Kp. (2 mm) = 73°C. - NMR (CCl4):δ= 0.92, s, 6H (2,2-CH3), 2.68, s (CH2-3), 7.0-7.4, m (Phenyl-H), 9.65 ppm, s (CH-1). - IR: 1730, 2740 cm-1 (Aldehyd). - MS: m/e (%) = 162 (20, M+), 147 (4), 133 (7), 115 (5), 105 (4), 91 (100). C11H14O (162, 2).A solution of 224 g (4 mol) of KOH and 10 g of tricapryl-methyl-ammonium chloride (Aliquat 336) in 125 g of water was mixed with 200 ml of toluene and heated to boiling. With continued boiling, a solution of 402 g (3.2 mol) of benzyl chloride (7) and 256 g (3.6 mol) of isobutyraldehyde was added dropwise over the course of 1 hour. After stirring for 7 hours at boiling point. and cooling to room temp. was thinned with 300 g of water. The aqueous phase was extracted with toluene. The combined organic phases were washed neutral and concentrated. The crude product (510 g of yellow oil) gave 354 g (69%) as a colorless oil when distilled through a 60 cm glass packed column. Kp. (2 mm) = 73 ° C. - NMR (CCl 4 ): δ = 0.92, s, 6H (2,2-CH 3 ), 2.68, s (CH 2 -3), 7.0-7.4, m (phenyl-H), 9.65 ppm, s (CH -1). - IR: 1730, 2740 cm -1 (aldehyde). - MS: m / e (%) = 16 2 ( 2 0, M + ), 1 4 7 (4), 133 (7), 115 (5), 105 (4), 91 (100). C 11 H 14 O (162, 2 ).

Beisviel 2So much 2 Darstellung von 2,2-Dimethyl-3-phenyl-propanol (1b):Preparation of 2,2-dimethyl-3-phenyl-propanol (1b):

In einem Autoklaven wurden 354 g 2,2-Dimethyl-3-phenyl-propanal (la)mit 2 g Kupferchromit (G-79) bei 150°C und 120 bar bis zur Aufnahme von 1 Äquivalent Wasserstoff hydriert. Nach Entspannen des Autoklaven wurde der Katalysator abgetrennt. Destillation über eine 60 cm Füllkörperkolonne ergab 320 g (90 %) 2,2-Dimethyl-3-phenyl-propanol (1b) als farbloses, erstarrendes Öl. Kp. (2 mm) = 90°C, Schmp. 34-36°C. - NMR (CCl4):δ= 0.88, s, 6H (2,2-CH3), 2.55, s (CH2-3), 3.37, s (CH2-1), 7.1- 7.3, br.s (Phenyl-H). - IR: 3400 cm-1 (0-H). - MS: m/e (%) = 164 (16, M+), 133 (5), 131 (4), 117 (6), 115 (8), 105 (4), 92 (100), 91 (83). C11H16O (164.2).354 g of 2,2-dimethyl-3-phenyl-propanal (la) were hydrogenated in an autoclave with 2 g of copper chromite (G-79) at 150 ° C. and 120 bar until 1 equivalent of hydrogen was taken up. After releasing the pressure in the autoclave, the catalyst was separated off. Distillation over a 60 cm packed column resulted in 320 g (90%) of 2,2-dimethyl-3-phenyl-propanol (1b) as a colorless, solidifying east l. Kp. ( 2 mm) = 90 ° C , mp. 34-36 ° C. - NMR (CCl 4): δ = 0.88, s, 6H (2,2-CH 3), 2.55 s (CH 2 -3), 3.37 s (CH 2 -1), 7.1. 7 3 , br . s (phenyl- H ). - IR: 340 0 cm -1 (0-H). - MS: m / e (%) = 164 (16, M + ), 133 (5), 131 (4), 117 (6), 115 (8), 105 (4), 92 ( 10 0), 91 (83). C 11 H 16 O (164.2).

Beispiel 3Example 3 Darstellung von 2,2-Dimethyl-3-phenyl-propyl-l-acetat (1c):Preparation of 2,2-dimethyl-3-phenyl-propyl-1-acetate (1c):

Eine Lösung von 100 ; 2,2-Dimethyl-3-phenyl-propan-1-ol (1b) und 20 g Natriumacetat in 100 g Essigsäureanhydrid wurde 3 Stdn. zum Sieden erhitzt. Nach üblicher Aufarbeitung wurde das Rohprodukt (l05 g hellgelbes Öl) über eine 30 cm Glasfüllkörperkolonne destilliert. Man erhielt 90 g 1C als farbloses Öl. Kp (2 mm) = 90°C. - NMR (CCl4): δ = 0.87, s, 6H (2,2-CH3), 1.98, s (-O-CO-CH3), 2.53, s (CH2-3), 3.73, s (CH2-1), 6.9-7.2 ppm, m (Phenyl-H). - IR: 1735 cm-1 (Acetat).-MS: m/e (%): 206 (M+), l46 (27), 131 (22), 115 (16), 9l (35), 43 (100).A solution of 100; 2,2-Dimethyl-3-phenyl-propan-1-ol (1b) and 20 g sodium acetate in 100 g acetic anhydride were heated to boiling for 3 hours. After the usual work-up, the crude product (105 g of light yellow oil) was distilled through a 30 cm glass packed column. 90 g of 1C were obtained as a colorless oil. Kp (2 mm) = 90 ° C. - NMR (CCl 4 ): δ = 0.87, s, 6H (2,2-CH 3 ), 1.98, s (-O-CO-CH 3 ), 2.53, s (CH 2 -3), 3.73, s ( CH 2 -1), 6.9-7.2 ppm, m (phenyl-H). - IR: 1735 cm -1 (acetate) .- MS: m / e (%): 2 06 (M + ), l46 (27), 131 (22), 115 (16), 9l (35), 43 ( 100).

C13H18O2 (206.3).C 13 H 18 O 2 (206.3).

Beispiel 4Example 4 Darstellung von 2,2-Dimethyl-3-phenyl-propionitril (ld):Preparation of 2,2-dimethyl-3-phenyl-propionitrile (ld):

Bei 20-30°C wurdeneiner Lösung von 22.7 g (0.25 mol) Hydroxylaminhydrogensulfat in 40 mℓ Methanol und 20 mℓ Wasser unter Rühren 36 g wässrige Natronlauge (33 %) zugegeben. Anschliessend ließ man 40.5 g (0.25 mol) 2,2-Dimethyl-3-phenyl-propanal (la)zulaufen und rührte die Reaktionsmischung 3 Stdn. bei Raumtemperatur. Zur Aufarbeitung wurde mit 150 mℓ Wasser ausgedünnt und mit Methylenchlorid extrahiert. Nach Einengen verblieben ca. 45 g Oxim 9, die innerhalb von 20 min zu 80 g siedenden Acetanhydrids hinzugegeben wurden. Nach 5 Stdn. Rühren bei Siedetemp. wurde mit 200 mℓ Wasser ausgedünnt, mit Benzin extrahiert und eingeengt. Destillation des Rohprodukts (6.40 g) über eine kurze Kolonne und anschließende Kristallisation aus Ethanol ergab 20 g 1d vom Schmp. 55-56°C. - NMR (CCl4):δ= 1.27, s, 6H (2,2-CH3), 2.71, s (CH2-3), 7.1-7.3 PPm (Phenyl-H). - IR: 2230 cm-1 (Nitril). - MS: m/e (%) = 159 (11, M+), 146 (3), 132 (3), 117 (6), 115 (3), 91 (100), 65 (9). C11H13N (159.2).At 20-30 ° C, 36 g aqueous sodium hydroxide solution (33%) was added to a solution of 22.7 g (0.25 mol) hydroxylamine hydrogen sulfate in 40 ml methanol and 20 ml water with stirring. Then 40.5 g (0.25 mol) of 2,2-dimethyl-3-phenyl-propanal (Ia) were run in and the reaction mixture was stirred for 3 hours at room temperature. For working up, the mixture was diluted with 150 ml of water and extracted with methylene chloride. After concentration, about 45 g of oxime 9 remained, which were added to 80 g of boiling acetic anhydride within 20 minutes. After stirring for 5 hours at boiling point. was thinned with 200 mℓ of water, extracted with gasoline and concentrated. Distillation of the crude product (6.40 g) over a short column and subsequent crystallization from ethanol gave 20 g 1d of mp 55-56 ° C. - NMR (CCl 4 ): δ = 1.27, s, 6H (2,2-CH 3 ), 2.71, s (CH 2 -3), 7.1-7.3 PPm (phenyl-H). - IR: 2230 cm -1 (nitrile). - MS: m / e (%) = 159 (11, M + ), 146 (3), 1 32 (3), 117 (6), 11 5 (3), 91 (100), 6 5 (9). C 11 H 13 N (159.2).

Beispiel 5Example 5 Parfümöl mit Maiglöckchen-DuftPerfume oil with lily of the valley fragrance

Figure imgb0005
Das Parfümöl der Mischung a besitzt einen ausgewogenen Maiglöckchen-Duft. Die Mischung b, in der anstelle des Carbinols 3 der erfindungsgemäße Alkohol 1b eingesetzt wurde, besitzt ebenfalls einen harmonischen Maiglöckchen-Duftkomplex, der sich jedoch gegenüber der Mischung a durch mehr Fülle und natürliche Ausstrahlung auszeichnet.
Figure imgb0005
 The perfume oil of mixture a has a balanced lily of the valley fragrance. The mixture b, in which the alcohol 1b according to the invention was used instead of the carbinol 3, also has a harmonious lily of the valley fragrance complex, which, however, is distinguished from the mixture a by more body and natural charisma.

Beispiel 6Example 6 Parfümöl mit Fougère-NotePerfume oil with a fougère note

Figure imgb0006
Das Parfümöl der Mischung a hat einen Duftkomplex vom Fougere-Typ mit holzigen, herb-süßen Aspekten. Das Parfümöl b, das zusätzlich die neue Verbindung 1c enthält, besitzt einen Duftkomplex ähnlichen Typs, in dem jedoch eine süß-pudrige Note betont wird und der zugleich deutlich abgerundet und harmonischer wirkt.
Figure imgb0006
 The perfume oil of mixture a has a fragrance complex of the fougere type with woody, bitter-sweet aspects. The perfume oil b, which also contains the new compound 1c, has a fragrance complex of a similar type, in which, however, a sweet-powdery note is emphasized and which at the same time has a clearly rounded and harmonious effect.

BeisDiel 7Bei D iel 7 Parfümöl "Flieder"Perfume oil "lilac"

Figure imgb0007
Das Parfümöl a besitzt einen ausgewogenen Flieder-Duft. Das durch Austausch des geruchlosen Dipropylenglykol und Einsetzen von 15 % des Carbinols 1b erhaltene Parfümöl hat einen noch stärker ausstrahlenden und natürlich wirkenden Fliederduft. Die Einarbeitung von 5 % des Nitrils ld führt unter Betonung der krautig-grünen Aspekte zu einem originellen blumig-frischen Duftkomplex.
Figure imgb0007
 Perfume oil a has a balanced lilac scent. The perfume oil obtained by replacing the odorless dipropylene glycol and using 15% of carbinol 1b has an even more intense and natural-looking lilac scent. The incorporation of 5% of the nitrile ld leads to an original floral-fresh fragrance complex, emphasizing the herb-green aspects.

Beispiel 8Example 8 Parfümöl mit pudrig-süßem CharakterPerfume oil with a powdery-sweet character

Figure imgb0008
Das Parfümöl der Zusammensetzung a besitzt eine klassische süß-pudrige Note mit holzigen und würzigen Aspekten. Die durch Zugabe des erfindungsgemäßen Nitrils 1d erhaltene Mischung b wirkt harmonischer und weicher unter gleichzeitiger Betonung süß-würziger Nebennoten. Durch Zugabe von 5 % des erfindungsgemäßen Aldehyds la (Mischung c) wurde ein neuer Duftakkord erhalten, der sich durch frische Ausstrahlung bei holzig-süßem Grundgeruch und grün-krautigen Nebennoten auszeichnet.
Figure imgb0008
 The perfume oil of composition a has a classic sweet-powdery note with woody and spicy aspects. The mixture b obtained by adding the nitrile 1d according to the invention has a more harmonious and softer effect while emphasizing sweet-spicy side notes. By adding 5% of the aldehyde la according to the invention (mixture c), a new fragrance chord was obtained which is characterized by a fresh radiance with a woody-sweet basic smell and green-herbaceous side notes.

Beisniel 9Example 9 Darstellung von 2-Ethyl-2-benzyl-hexanal-1 (11a):Preparation of 2-ethyl-2-benzyl-hexanal-1 (11a):

In Analogie zu der in Beispiel 1 gegebenen Vorschrift wurde aus Benzylchlorid (7) und a-Ethylhexanal (10) der Aldehyd lla in einer Ausbeute von 62 % als farbloses Öl gewonnen. Kp (2mm) = 110°C. - NMR (CCl4): δ = 0.84, t, 6H (-CH2-CH3), 2.75, s (Ø-CH2-), 7.0-7.2, m (aromat. H), 9.7 PPm (-CHO). - IR:2750, 1725 cm-1 (Aldehyd). - MS: m/e (%) = 218 (2, M+), 189 (6), 162 (7), 161 (7), 133 (4), 119 (5), 105 (7), 92 (18), 91 (100). C15H22O (218.3).In analogy to the procedure given in Example 1, the aldehyde IIIa was obtained from benzyl chloride (7) and α-ethylhexanal (10) in a yield of 62% as a colorless oil. Kp (2mm) = 110 ° C. - NMR (CCl 4 ): δ = 0.84, t, 6H (-CH 2 -CH 3 ), 2.75, s (Ø-CH 2 -), 7.0-7.2, m (aromatic H), 9.7 PP m (- CHO). - IR: 2750, 1725 cm -1 (aldehyde). - MS: m / e (%) = 218 (2, M + ), 189 (6), 16 2 (7), 161 (7), 133 (4), 1 1 9 (5), 105 (7) , 9 2 ( 1 8), 9 1 (100). C 15 H 22 O (218.3).

Beispiel 10Example 10 Darstellung von 2-Ethyl-2-benzyl-hexanol-l (llb):Preparation of 2-ethyl-2-benzyl-hexanol-l (llb):

In Analogie zu der in Beispiel 2 gegebenen Vorschrift wurde aus lla der Alkohol llb in einer Ausbeute von 90 % als farbloses Öl mit Kp (2 mm) = 125°C erhalten. NMR (CCl4): δ= 0.88, br. t, CH (-CH2-CH3), 2.58, s (Ø - CH2-), 3.25, s (-CH2-OH), 7.13 ppm, s (aromat. H). - IR: 3400 cm-1 (OH). - MS: m/e (%) = 220 (4, M+), 128 (12), 92 (100), 9l (62), 69 (47). C15H24O (220.3).In analogy to the procedure given in Example 2, the alcohol IIb was obtained from lla in a yield of 90% as a colorless oil with bp (2 mm) = 125 ° C. NMR (CCl 4 ): δ = 0.88, br. t, CH (-CH 2 -CH 3 ), 2.58, s (Ø - CH 2 -), 3.25, s (-CH 2 -OH), 7.13 ppm, s (aromat. H). - IR: 3400 cm -1 (OH). - MS: m / e (%) = 220 (4, M + ), 128 (12), 92 (100), 9l (62), 69 (47). C 15 H 24 O (220. 3).

Beispiel 11Example 11 Parfümöl mit frischer Agrumen-NotePerfume oil with a fresh note of agrumen

Figure imgb0009
Figure imgb0010
Dieses Parfümöl besitzt einen harmonischen Geruchskomplex vom Agrumen-Typ mit frischen grün-krautigen Noten. Nach Zugabe von 100 Teilen 2-Benzyl-2-ethyl-hexanal (lla) wirkt das Parfümöl feiner und natürlicher. gleichzeitig erfährt der Duftkomplex eine deutliche Fixierung.
Figure imgb0009
Figure imgb0010
 This perfume oil has a harmonious smell complex of the agrumen type with fresh green-herbaceous notes. After adding 100 parts of 2-benzyl-2-ethyl-hexanal (Ila), the perfume oil looks finer and more natural. at the same time, the fragrance complex is clearly fixed.

Claims (1)

Verwendung von 1,1-Di(C1-C6-alkyl)-2-phenyl-ethanDerivaten der Formel A, wobei R eine Formyl-, Hy-
Figure imgb0011
droxymethyl-, Formoxymethyl-, Acetoxymethyl oder Nitrilgruppe bedeutet und die Gesamtzahl der Kohlenstoffatome in den beiden Alkylsubstituenten zusammen maximal 8 beträgt, als Riechstoffe oder Bestandteil von Parfüm-Kompositionen für kosmetische oder technische Parfümierungen.Use of 1,1-di (C 1 -C 6 alkyl) -2-phenylethane derivatives of the formula A, where R is a formyl, hy-
Figure imgb0011
 Droxymethyl, formoxymethyl, acetoxymethyl or nitrile group and the total number of carbon atoms in the two alkyl substituents is a maximum of 8, as fragrances or as a component of perfume compositions for cosmetic or technical perfuming.
EP19820109101 1981-10-02 1982-10-01 Use of 1,1-di(c1-c6-alkyl)-2-phenyl-ethane derivatives as aroma chemicals Expired EP0076493B1 (en)

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DE440362T1 (en) * 1990-02-02 1992-06-11 International Flavors & Fragrances Inc., New York, N.Y. 2-2-DIMETHYL-1-NITRILO OR 2,2-DIMETHYL-1-HYDROXYLAMINO-3- (ALKYLPHENYL) SUBSTITUTED PROPANE OR 2-METHYL-1-NITRILO- OR 2-METHYL-1-HYDROXYLAMINO ) PROPANE, YOUR ORGANOLEPTIC USE AND METHOD FOR THEIR PRODUCTION.
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US20130273619A1 (en) 2012-04-16 2013-10-17 Basf Se Process for the Preparation of (3E, 7E)-Homofarnesol

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Cited By (20)

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EP0144815A1 (en) * 1983-11-17 1985-06-19 Consortium für elektrochemische Industrie GmbH Alpha-tertiary dimethyl acetals, their preparation and use as perfumes
EP0270841A2 (en) * 1986-11-15 1988-06-15 BASF Aktiengesellschaft 2-Methyl-3-(para-methyl-phenyl) propionitrile, its preparation and use as a perfuming agent
EP0270841A3 (en) * 1986-11-15 1988-07-20 BASF Aktiengesellschaft 2-methyl-3-(para-methyl-phenyl) propionitrile, its preparation and use as a perfuming agent
EP0275434A1 (en) * 1986-12-29 1988-07-27 Kuraray Co., Ltd. 2-Cyano-4-phenyl pentane and fragrance or perfume compositions containing the same
US4837351A (en) * 1986-12-29 1989-06-06 Kuraray Company Ltd. 2-cyano-4-phenyl pentane and fragrance or perfume compositions containing the same
WO1988005770A1 (en) * 1987-02-06 1988-08-11 Consortium für elektrochemische Industrie GmbH Alcohols with 3-methyl or 3,5-dimethyl groups their production and their use as aromatics
EP0287084A2 (en) * 1987-04-15 1988-10-19 Consortium für elektrochemische Industrie GmbH Alcohols containing 2-methyl or 2-methoxyphenyl groups, and their use as flavouring agents
EP0287084A3 (en) * 1987-04-15 1989-05-03 Consortium Fur Elektrochemische Industrie Gmbh Alcohols containing 2-methyl or 2-methoxyphenyl groups, and their use as flavouring agents
US4990494A (en) * 1990-02-02 1991-02-05 International Flavors & Fragrances Inc. 1,1-dimethyl-1-nitrilo or hydroxylamino-3-(alkyl phenyl)-substituted propanes, organoleptic uses thereof and processes for preparing same
EP0531636A1 (en) * 1991-09-13 1993-03-17 INTERNATIONAL FLAVORS & FRAGRANCES INC. Process for preparing phenyl butyronitriles and perfumery use of 2,2-dimethyl-4-phenyl valeronitrile
EP0678496A1 (en) * 1994-04-15 1995-10-25 INTERNATIONAL FLAVORS & FRAGRANCES INC. Reduced reaction product of protonic acid catalyzed reaction of methyl ethyl ketone and benzaldehyde and perfume uses thereof
US5389608A (en) * 1994-05-12 1995-02-14 International Flavors & Fragrances Inc. 1-phenyl-1-cyano-C5 -C7 alkanes, organoleptic uses thereof and process for preparing same
WO1997016512A1 (en) * 1995-11-01 1997-05-09 Givaudan-Roure (International) S.A. Nitrile
WO2000001360A1 (en) * 1998-07-07 2000-01-13 Quest International B.V. Perfume compositions
US6475473B1 (en) 1998-07-07 2002-11-05 Quest International B.V. Perfume compositions
US8236339B2 (en) 2001-05-15 2012-08-07 Hemocorm Limited Therapeutic delivery of carbon monoxide
US7964220B2 (en) 2002-02-04 2011-06-21 ALFAMA—Investigação e Desenvolvimento de Produtos Farmacêuticos, Lda. Method for treating a mammal by administration of a compound having the ability to release CO
US7968605B2 (en) 2002-02-04 2011-06-28 ALFAMA—Investigação e Desenvolvimento de Produtos Farmacêuticos, Lda. Methods for treating inflammatory disease by administering aldehydes and derivatives thereof
US7989650B2 (en) 2002-11-20 2011-08-02 Hemocorm Limited Therapeutic delivery of carbon monoxide to extracorporeal and isolated organs
US9611286B2 (en) 2011-07-21 2017-04-04 Alfama, Inc. Ruthenium carbon monoxide releasing molecules and uses thereof

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EP0076493A3 (en) 1985-01-09
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DE3139358A1 (en) 1983-04-21

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